Manipulation and storage of bromine



Patented Feb. 23, 1954 MBNIBUIJHTIONHNDSTORAGE F BROMINE Rildol BIoch, Isaac Schnerb, and David Kaplan,

Jerusalem, Israel Cla'imsmriority;application France September 25,'-1948-i1'7:

This'iifizentionirelates tolthe.manipulationand; storageof bromine.

Elementa'rsn. bromine is difiicult'to manipulate and ltol-ke'epin storage in leaden vessels (which term,, .in..this specification and the appended claims, is intended to include lead-coated vessels made-from other-materials), ioralthough fundamentally inert. towardsrlead, yet in .pr;actice the bromine ten'ds'toworro'devesselsinwhich it is storedionsubj ected to certain manipulations; e. g. 1' 1 0 disfillafifl'nfml'; condensation. Thus, it has been found thateleaden..storagenvesselsi are suddenly perforated by .the bromine after some: *time, thkiugl iinzmanyl. cases no apparent .a damage "had: occurred; even for .weeks. ...This; destructiom' for which no rexplanation. i could. be: iound so. far;- taleesr place:even .where. the vessel's'i's made from exceptionally pure. IeacL. Nor has careful drying oftth bromine and. exclusiomof:moisture been otanyavailnh For the aforesaidlreason it is customary to store and handle bromine in glass or earthenware vessels) These are more expensive and breakablethan =leaden=wessels and cannot conveniently be made as largerasrthelatterer It EWOllld, therefore, be preferable.to.luse.leaden vessels if the cor,- rosionthereofxiould ibeprevented.

The invention hasas its*object to provide a mannenof storing or manipulating bromine in" leaden. vessels without damage totthei latterl- The invention is based vJon the new discovery that" the aforesaid attack "of bromine; onfllead' .is brought aboutsandicatalysed by therpresenoe of hydrogen br'omideand that inltheicompletei absenceof hydrogen,brbmideinosuch .attack'lde velops.- The hydrogen bromide appears to dis.-. solve the. metalwithr-the formatiornof bromide andoi hydrogenwhich.reecombiiies with another portion of bromine whereby fresh hydrogen br'o"-. mideis iormed Now, any .kind ofimpurity. have" ingzga reducingaction. on the; bromine? is a' potential'source-of hydrogen bromide. Ofdilialtllv dust-.may .aotoin this-direction, or ..fragments of organicamatter like ,.wood, cork. or: rubber t. derives ing from stoppers or plugs, or gaseous -.ag.ents ,v-- r such:; as ahydrogenssulfide or carbonemonoxide in the presencetof vmoisture:or.

Based on this new discovery the present invention consists therein that the bromine is kept in storage or subjected to distillation or other manipulation in leaden vessels in the presence of an oxidizing agent adapted to decompose hydrogen bromide with the formation of elementary bromine. The oxidizing agent may be distributed throughout the liquid bromine or be the reactionwof: a small-proportion-of .the-totale-i Forlexamplerlead peroxide is particularlyssui able asaanaoxidizinglagent sinceiit-cane-be genere e ated o'rrthe:surcfaceofithe-leadwalls otthe vesselei by anodic oxidation.

Other metal oxides come equally into regard for the purposes of thisinvention, e. g. mangan'ese 'dioxidel 1 Anothn'iclass :tof t-suitable i oxidizing: :agents 5 formedabyitlre .asaltsiofiryarious .oxygen-cacids lofbromine; e. :g. bromates-:andshypobromitessrz: They mayebe added to the bromine in theiormaof 811 aqueousrzsoluti'onsupernatant.on theEbrominemr bezgeneratedi within the vessel'r'by I the .additionrzto' thetbrbmine ofia supernatantflayenof analkaqae line reacting;vaqueousnliquor;z e. @g. :a sodiumie'or potassium hydroxide, carbonate or bicarbonate solution, or a calciuin hydroxide suspension, wherein -elementary-' bromine dissoivesrwith the formationmn the: one hand foftbromide, rand-1 cm: the other 'ihand bf hypobcrornite and" ultimately'x; broma'tei- OIY'GISGF' the: oxidizing z substartce :'-may: be disposed in" soli'd' form-" 1in the spaceasofathewesse v abdve the" liq'uid bromineslevelre. g. ;o atrays orf in ba'skets 'suspen'dedvthereingtorzcbnr wail'lialpr jec-tionszl-fln such' a case one'imay usepiorrexampleiz metalseoxides'eor peroxidesPas aforesaid,fror xelsew arr alkaline reacting lsubstanceccapable of former: in'g= hypobr'omite by :theiactionrtofi gaseousebr' mine e. g. calciuinsoxide'.onihydroxida sodium'z'or potassium-bicarbonate:or carbonate in luinpsrorwr fragments; or the likexa Experiments have shown conclusivelyithatebyt r the presence of the oxidizing agents adapted stantaneouslylto decomposes anynchydrogenzzbroiemide -present br" forming: init'th'etrvesselsleademn manipulating and' "storage vessels: oant'ibew made to with's'tanditheaction of ibromine :for'ra virtually unlimited: time -'evenwund'erisuch conditionsn asm v would riormally be conducive'to .a rapidrzoorrosi'omt of"-th'e'"lead hamelyj'iinitheipresenee'zof:reducingtra agentstparticdlarly iragmentsiof organie matteres: or I-IzS.

This invention is illustrated by the following examples to which it is, of course, not limited.

Example 1 Into a cylindrical storage tank with cambered bottom, having a capacity of 4 cubic meters and a diameter of 2 meters made from iron and lined internally with lead, bromine and a 5% aqueous solution of potassium bromate are introduced. It is preferred first to pour in the bromate solution and thereafter the bromine. A suitable amount of bromate solution is 5 liters per square meter of bromine surface.

The example may be modified thereby that the bromate solution is replaced by a 1 N aqueous sodium or potassium hydroxide solution.

Example 2 A bromine transport flask of iron lined with a coat of lead 1 mm. thick, is filled with N aqueous sulfuric acid and connected to the positive pole of a source of direct current. A lead rod connected to the negative pole of the source of current is inserted through the neck into the flask without contact therewith. Direct current is then passed at about 4 volts through the flask until the lead coat has assumed brown colouring due to the formation of lead peroxide. The current is then switched on", the negative electrode removed from the flask, the sulfuric acid poured out, and the flask is rinsed with water and dried, then the bromine to be stored or transported is introduced therein. It is advantageous to pretreat the bromine by allowing it to run through a tower containing lead oxide in pieces, or by making a 5% aqueous bromate solution bubble through the bromine.

Example 3 A perforated cylindrical lea-d cage is suspended in a lead-coated iron bromine storage tank. The

cage is filled with granulated lead peroxide, or r.

crystalline potassium bromate, or lumps of calcium bromide-hypobromite (the bromine analogue of bleaching powder), its perforations being made so large only as not to alloy. the granules, crystals or lumps to fall out. The tank is then ready to receive the bromine to be stored.

Example 4 An apparatus for the distillation of bromine,

either for purification or in order to separate it from mixtures containing or developing it, may

comprise a leaden boiling vessel and a descending lead condenser. The usual rapid corrosion of the container and condenser is prevented according to the invention in a twofold manner:

The boiling mixture in the container is admixed with so much of an aqueous bromate solution or a leadv peroxide sludge, or a suspension of bromate cry; sis in bromine, that the mixture contains substantially one equivalent amount of active oxygen for each 100 equivalent amounts elemental bromine at atmospheric conditions and selected from the group consisting of PbOz, MnOz and salts of oxygen acids of bromine.

2, The method of claim 1 in which said compound is preformed and introduced as such into said vessel.

3. The method of claim 1 in which said compound is a bromate.

4. The method of claim 1 in which said compound is a hypobromite.

5. The method of claim 1 in which said compound is a salt of an oxygen acid of bromine, said salt being formed in said vessel by the reaction of bromine with alkaline reacting liquors selected from the group consisting of aqueous solutions of alkali hydroxides, carbonates and bicarbonates, and aqueous suspensions of calcium hydroxide.

6. The method of claim 1 in which said compound is a, salt of an oxygen acid of bromine and is formed by contact of the bromine with an added alkaline reacting compound.

RUDOLF BLOCH. ISAAC SCHNERB.

DAVID KAPLAN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 103,253 Stieren May 17, 1870 110,662 Juhler Jan. 3, 1871 181,617 Arvine Aug. 29, 1876 1,870,398 Behrman Aug. 9, 1932 1,885,029 Dressel Oct. 25, 1932 1,917,762 Grebe July 1, 1938 2,163,237 7 Hooker June 27, 1939 2,336,443 COX Dec. 7, 1943 2,380,254 McCullough July 10, 1945 2,472,635 Weber June 7, 1949 FOREIGN PATENTS Number Country Date 551,789 Great Britain Mar. 10, 1943 J. W. Mellors A Comprehensive Treatise on 7 Inorganic and Theoretical Chemistry, vol. 2, page 90; vol. 7, pages 573, 745. Longmans, Green and Co., N. Y.

Lowrys Inorganic Chemistry, 2nd ed., 1931, pp. 348, 349. MacMillan and Co., Ltd, London.

Chem. and Met. Eng, September 1944, page 112.

Langes Handbook of Chemistry, 4th ed., pages 8 and 9. Handbook Publishers, Inc., Sandusky, Ohio.

Materials for Bromine Containers, by George S. Haines, I. and E. Chem, vol. 41, No. 12, pages 2792-2794.

McPherson and Henderson A Course in General Chemistry, 3rd ed., pages 164, 366, 367, 640. Ginn and Co., N. Y.

Uhligs Corrosion Handbook, pp. 212-213, 1948 ed. John Wiley and Sons, Inc., N. Y. 

1. IN THE METHOD OF MAINTAINING LIQUID BROMINE IN A LEADEN VESSEL IN THE PRESENCE OF MOISTURE AND SUBSTANCES WHICH REDUCE BROMINE TO HYDROGEN BROMINE IN THE PRESENCE OF MOISTURE AT ATMOSPHERIC CONDITIONS THE STEP OF PREVENTING CORROSION OF SAID VESSEL WHICH COMPRISES ADDING TO SAID BROMINE AN OXYGEN-CONTAINING COMPOUND CAPABLE OF OXIDIZING HYDROGEN BROMIDE TO ELEMENTAL BROMINE AT ATMOSPHERIC CONDITIONS AND SELECTED FROM THE GROUP CONSISTING OF PBO2,MN02 AND SALTS OF OXYGEN ACIDS OF BROMINE. 